EP0089066B1 - Process for modifying the bonding of siloxane elastomer - Google Patents

Process for modifying the bonding of siloxane elastomer Download PDF

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Publication number
EP0089066B1
EP0089066B1 EP19830102615 EP83102615A EP0089066B1 EP 0089066 B1 EP0089066 B1 EP 0089066B1 EP 19830102615 EP19830102615 EP 19830102615 EP 83102615 A EP83102615 A EP 83102615A EP 0089066 B1 EP0089066 B1 EP 0089066B1
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EP
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Prior art keywords
cross
composition
water
linked
organopolysiloxane
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Expired
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EP19830102615
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German (de)
French (fr)
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EP0089066A1 (en
Inventor
Horst Höhl
Peter Dr. Kochs
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Wacker Chemie AG
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Wacker Chemie AG
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/50—Multilayers
    • B05D7/56—Three layers or more
    • B05D7/58—No clear coat specified
    • B05D7/586—No clear coat specified each layer being cured, at least partially, separately
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1693—Antifouling paints; Underwater paints as part of a multilayer system
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2202/00—Metallic substrate
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S528/00—Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S528/901—Room temperature curable silicon-containing polymer
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31652—Of asbestos
    • Y10T428/31663—As siloxane, silicone or silane

Definitions

  • the invention relates to a method for strengthening the adhesion of organopolysiloxane elastomers, which have been produced from masses that can be crosslinked at room temperature, to substrates by applying a primer to the base prior to the application of the mass that can be crosslinked to the elastomer, this mass in addition to diorganopolysiloxane that is crosslinkable , Crosslinking agent and catalyst, as at least one further constituent or as at least part of further constituents, a substance which is still flowable after the crosslinking of the composition, or rod-shaped copolymer of styrene and n-butyl acrylate, which is obtained by copolymerizing the monomers mentioned by means of free Radicals were generated in the presence of diorganopolysiloxane, or both such a copolymer and a substance which is still flowable after the crosslinking of the composition, and the crosslinking agent and catalyst in the composition only more or less shortly before application the mass on the primer are combined with
  • the method according to the invention is particularly important in the case of substrates which consist of solid surfaces which are under water containing water for so long that vegetation would form on them without treatment.
  • substrates which consist of solid surfaces which are under water containing water for so long that vegetation would form on them without treatment.
  • examples of such surfaces are those made of glass, wood, plastic, such as epoxy resin, including adhesive lacquers based on epoxy tar, or polyester reinforced with glass fiber, inorganic building material, such as concrete or metal, e.g. B. iron or steel from z.
  • inorganic building material such as concrete or metal, e.g. B. iron or steel from z.
  • the water containing living organisms to which the documents treated according to the invention can be exposed can be sea or fresh water, in particular sea water. The water can stand or flow.
  • Organopoysiloxane compositions which can be crosslinked at room temperature and into which the crosslinking agent and catalyst are mixed more or less shortly before their final use are so-called «two-component compositions» or «two-component systems •.
  • compositions which can be crosslinked to form organopolysiloxane elastomers and which, in addition to at least diorganopolysiloxane which can be crosslinked, contain crosslinking agents and catalyst in the form of a rod-shaped copolymer of styrene and n-butyl acrylate, by means of free-radical polymerization of the monomers mentioned, i.e. styrene and n-butyl acrylate
  • diorganopolysiloxane has been described many times and therefore need not be explained again here. This manufacture is e.g. B. in the above-mentioned US Pat. No.
  • the rod-shaped copolymers which were produced in the presence of diorganopolysiloxane by copolymerization using free radicals, consist 45 to 75 percent by weight of units derived from styrene and the rest of units derived from n-butyl acrylate.
  • the amount of diorganopolysiloxane is preferably 20 to 60 percent by weight, based on the total weight of diorganopolysiloxane and copolymer of styrene and n-butyl acrylate.
  • At least 80% of the number of organic residues in the diorganosiloxane units is preferably methyl residues.
  • the diorganopolysiloxanes in the presence of which rod-shaped copolymer of styrene and n-butyl acrylate are produced, preferably have an average viscosity of 150 to 6000 mPa.s at 25 ° C.
  • the substance which is still flowable after the crosslinking of the organopolysiloxane mass to form the elastomer can be diorganopolysiloxane which is liquid at room temperature and is blocked by triorganosiloxy groups (cf. GB-PS 14 70 465, published April 14, 1977, The International Paint Company Limited). or are flowable organic compounds free of metal and silicon (cf. DE-OS 2756495, published June 22, 1978, Shell International Research Maatschappij BV) or else mixtures of such flowable organic compounds and flowable organopolysiloxanes.
  • triorganosiloxy end-blocked diorganopolysiloxanes are trimethylsiloxy endblocked dimethylpolysiloxanes end-blocked by trimethylsiloxy methyl phenyl end-blocked by trimethylsiloxane copolymers of dimethylsiloxane and methylphenylsiloxane endblocked by trimethylsiloxy copolymers of dimethylsiloxane and diphenylsiloxane and end-blocked by trimethylsiloxy copolymers of dimethylsiloxane, Methylphenylsiloxane and diphenylsiloxane units.
  • flowable organic compounds free of metal and silicon are polyisobutylenes with a molecular weight of 350 and technical white oil as well as tricresyl phosphate.
  • the substance which is still flowable after the crosslinking of the organopolysiloxane composition to give the elastomer is preferably in this composition in amounts of 10 to 80 percent by weight, based on the total weight of such material, of the organopolysiloxane to be crosslinked and any rod-shaped copolymer of styrene and n-butyl acrylate present , available.
  • crosslinkers in two-component compositions of the type used in the context of the invention are polyethylene silicate with an SiO 2 content of 34 to 40% by weight and hexaethoxydisiloxane.
  • catalysts in two-component compositions of the type used according to the invention are tin compounds, such as dibutyltin dilaurate and dibutyltin diacrylates, the acrylate groups each being composed of a mixture of carboxylic acids having 9 to 11 carbon atoms per molecule, in which the carboxyl group is bonded to a tertiary carbon atom in at least 90 percent by weight of the acids is derived (so-called «dibutyltin diversate»).
  • organopolysiloxane polymer which has been prepared from a composition which can be stored with the exclusion of water and which crosslinks when water is admitted at room temperature is also known and has been described many times. Therefore, it does not have to be explained here either.
  • Such compositions are also commercially available.
  • Preferred among the masses which can be stored in the absence of water and which crosslink when water is admitted at room temperature are those which, when crosslinked, release acetic acid or amine, such as sec-butylamine or cyclohexylamine.
  • the primers used in the process according to the invention can be dissolved or dispersed in an organic solvent, such as toluene or a mixture of xylene isomers.
  • an organic solvent such as toluene or a mixture of xylene isomers.
  • the two-component compositions which can be crosslinked to give organopolysiloxane elastomers in the process according to the invention can be dissolved or dispersed in an organic solvent, such as white spirit.
  • the application of the mixtures used in the process according to the invention on the documents can, for. B. by brushing, pouring, spraying or rolling.
  • the arrangement obtained in this way is stored for 7 days at 23 ° C. and a relative water content of the air (“air humidity •) of 50%.
  • the sheet metal strip is then removed at a speed of 200 mm / minute.
  • the determined shear adhesion is 116 N / cm 2 .
  • the shear adhesion determined in the example after seven days of storage at 23 ° C. and 50% atmospheric humidity, is 92.4 N / cm 2 .

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Laminated Bodies (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Paints Or Removers (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Lining Or Joining Of Plastics Or The Like (AREA)

Description

Als Stand der Technik auf dem Gebiet der Verstärkung des Haftens von Organopolysiloxanelastomeren auf Unterlagen, auf denen diese Elastomeren erzeugt wurden, mittels einer Grundierung, wobei die so erhaltenen Verbunde der Einwirkung von Wasser ausgesetzt sind, wird US 4133 938 (veröffentlicht 9. Januar 1979, Th. G. Bingham, SWS Silicones Corporation) genannt.As prior art in the field of strengthening the adhesion of organopolysiloxane elastomers to substrates on which these elastomers were produced by means of a primer, the composites thus obtained being exposed to the action of water, US 4133 938 (published January 9, 1979, Th. G. Bingham, SWS Silicones Corporation).

Gegenstand der Erfindung ist ein Verfahren zum Verstärken des Haftens von Organopolysiloxanelastomeren, die aus bei Raumtemperatur vernetzbaren Massen hergestellt wurden, auf Unterlagen durch Auftragen einer Grundierung auf die Unterlage vor dem Auftragen der zum Elastomeren vernetzbaren Masse, wobei diese Masse zusätzlich zu Diorganopolysiloxan, das vernetzbar ist, Vernetzungsmittel und Katalysator, als mindestens einen weiteren Bestandteil bzw. als mindestens einen Teil weiterer Bestandteile einen Stoff, der nach dem Vernetzen der Masse noch fließfähig ist, oder stäbchenförmiges Mischpolymerisat aus Styrol und n-Butylacrylat enthält, das durch Mischpolymerisation der genannten Monomeren mittels freier Radikale in Gegenwart vom Diorganopolysiloxan erzeugt wurde, oder sowohl derartiges Mischpolymerisat als auch einen Stoff, der nach dem Vernetzen der Masse noch fließfähig ist, enthält und wobei Vernetzungsmittel und Katalysator in der Masse erst mehr oder weniger kurz vor dem Auftragen der Masse auf die Grundierung miteinander vereinigt werden, dadurch gekennzeichnet, daß als Grundierung eine Schicht, die zumindest teilweise aus vernetztem Organopolysiloxan aus SiO4/2-Einheiten, Trimethylsiloxaneinheiten und Vinyldimethylsiloxaneinheiten besteht und eine auf dieser Schicht aufgetragene und mindestens teilweise vernetzte Schicht aus Organopolysiloxanelastomer, das aus unter Ausschluß von Wasser lagerfähiger, bei Zutritt von Wasser bei Raumtemperatur vernetzender Masse hergestellt wurde, verwendet wird.The invention relates to a method for strengthening the adhesion of organopolysiloxane elastomers, which have been produced from masses that can be crosslinked at room temperature, to substrates by applying a primer to the base prior to the application of the mass that can be crosslinked to the elastomer, this mass in addition to diorganopolysiloxane that is crosslinkable , Crosslinking agent and catalyst, as at least one further constituent or as at least part of further constituents, a substance which is still flowable after the crosslinking of the composition, or rod-shaped copolymer of styrene and n-butyl acrylate, which is obtained by copolymerizing the monomers mentioned by means of free Radicals were generated in the presence of diorganopolysiloxane, or both such a copolymer and a substance which is still flowable after the crosslinking of the composition, and the crosslinking agent and catalyst in the composition only more or less shortly before application the mass on the primer are combined with one another, characterized in that the primer is a layer which consists at least partially of crosslinked organopolysiloxane composed of SiO 4/2 units, trimethylsiloxane units and vinyldimethylsiloxane units and a layer of organopolysiloxane elastomer applied and at least partially crosslinked on this layer, which has been prepared from mass which is storable with the exclusion of water and which crosslinks when water is admitted at room temperature.

Das erfindungsgemäße Verfahren hat besonders große Bedeutung bei Unterlagen, die aus Festkörperoberflächen bestehen, die sich so lange unter Lebewesen enthaltendem Wasser befinden, daß sich auf ihnen ohne Behandlung Bewuchs bilden würde. Beispiele für derartige Oberflächen sind solche aus Glas, Holz, Kunststoff, wie Epoxyharz, einschließlich Haftlacken auf der Basis Epoxid-Teer, oder mit Glasfaser verstärktem Polyester, anorganischem Baustoff, wie Beton oder Metall, z. B. Eisen bzw. Stahl, von z. B. Schiffsrümpfen, Bojen, Seeminen, den Pfeilern von Bohrinseln oder Brücken, von Behältern, einschließlich Badebecken, und Rohren. Bei dem Lebewesen enthaltendem Wasser, dem die erfindungsgemäß behandelten Unterlagen ausgesetzt werden können, kann es sich um Meer- oder Süßwasser, insbesondere Meerwasser handeln. Das Wasser kann stehen oder fließen.The method according to the invention is particularly important in the case of substrates which consist of solid surfaces which are under water containing water for so long that vegetation would form on them without treatment. Examples of such surfaces are those made of glass, wood, plastic, such as epoxy resin, including adhesive lacquers based on epoxy tar, or polyester reinforced with glass fiber, inorganic building material, such as concrete or metal, e.g. B. iron or steel from z. As ship hulls, buoys, sea mines, the pillars of oil rigs or bridges, containers, including bathing pools, and pipes. The water containing living organisms to which the documents treated according to the invention can be exposed can be sea or fresh water, in particular sea water. The water can stand or flow.

Bei Raumtemperatur vernetzbare Organopöiysiloxanmassen, in die Vernetzungsmittel und Katalysator mehr oder weniger kurz vor der endgültigen Verwendung eingemischt werden, sind sogenannte « Zweikomponentenmassen » oder « Zweikomponentensysteme •.Organopoysiloxane compositions which can be crosslinked at room temperature and into which the crosslinking agent and catalyst are mixed more or less shortly before their final use are so-called «two-component compositions» or «two-component systems •.

Die Herstellung von zu Organopolysiloxanelastomeren vernetzbaren Zweikomponentenmassen, die zusätzlich zu mindestens Diorganopolysiloxan, das vernetzbar ist, Vernetzungsmittel und Katalysator stäbchenförmiges Mischpolymerisat aus Styrol und n-Butylacrylat enthalten, das durch Mischpolymerisation der genannten Monomeren, also von Styrol und n-Butylacrylat, mittels freier Radikale in Gegenwart von Diorganopolysiloxan erzeugt wurde, ist vielfach beschrieben worden und muß daher hier nicht wieder näher erläutert werden. Diese Herstellung ist z. B. in der eingangs genannten US-PS 4 133 938, Beispiel 6, US 3 555 109 (veröffentlicht 12. Januar 1971, I. C. Getson, Stauffer-Wacker Silicone Corporation), Beispiel 6 und 8 und US 4 032 499 (veröffentlicht 28. Juni 1977, F.-H. Kreuzer et al., Consortium für Elektrochemische Industrie GmbH) Beispiel 6, eingehend beschrieben. Derartige Massen sind im Handel erhältlich.The preparation of two-component compositions which can be crosslinked to form organopolysiloxane elastomers and which, in addition to at least diorganopolysiloxane which can be crosslinked, contain crosslinking agents and catalyst in the form of a rod-shaped copolymer of styrene and n-butyl acrylate, by means of free-radical polymerization of the monomers mentioned, i.e. styrene and n-butyl acrylate The presence of diorganopolysiloxane has been described many times and therefore need not be explained again here. This manufacture is e.g. B. in the above-mentioned US Pat. No. 4,133,938, Example 6, US 3,555,109 (published January 12, 1971, IC Getson, Stauffer-Wacker Silicone Corporation), Examples 6 and 8 and US 4,032,499 (published 28. June 1977, F.-H. Kreuzer et al., Consortium für Elektrochemische Industrie GmbH) Example 6, described in detail. Such masses are commercially available.

Vorzugsweise bestehen die stäbchenförmigen Mischpolymerisate, die in Gegenwart von Diorganopolysiloxan durch Mischpolymerisation mittels freier Radikale erzeugt wurden, zu 45 bis 75 Gewichtsprozent aus sich von Styrol ableitenden Einheiten und zum Rest aus sich von n-Butylacrylat ableitenden Einheiten.The rod-shaped copolymers, which were produced in the presence of diorganopolysiloxane by copolymerization using free radicals, consist 45 to 75 percent by weight of units derived from styrene and the rest of units derived from n-butyl acrylate.

Vorzugsweise beträgt die Menge von Diorganopolysiloxan 20 bis 60 Gewichtsprozent, bezogen auf das Gesamtgewicht von Diorganopolysiloxan und Mischpolymerisat aus Styrol und n-Butylacrylat.The amount of diorganopolysiloxane is preferably 20 to 60 percent by weight, based on the total weight of diorganopolysiloxane and copolymer of styrene and n-butyl acrylate.

Insbesondere wegen der leichten Zugänglichkeit sind vorzugsweise mindestens 80 % der Anzahl der organischen Reste in den Diorganosiloxaneinheiten Methylreste.In particular because of the easy accessibility, at least 80% of the number of organic residues in the diorganosiloxane units is preferably methyl residues.

Vorzugsweise haben die Diorganopolysiloxane, in deren Gegenwart stäbchenförmiges Mischpolymerisat aus Styrol und n-Butylacrylat erzeugt wird, eine durchschnittliche Viskosität von 150 bis 6 000 mPa - s bei 25 °C.The diorganopolysiloxanes, in the presence of which rod-shaped copolymer of styrene and n-butyl acrylate are produced, preferably have an average viscosity of 150 to 6000 mPa.s at 25 ° C.

Bei dem Stoff, der nach dem Vernetzen der Organopolysiloxanmasse zum Elastomeren noch fließfähig ist, kann es sich um bei Raumtemperatur flüssige, durch Triorganosiloxygruppen endblockierte Diorganopolysiloxan (vgl. GB-PS 14 70 465, veröffentlicht 14. April 1977, The International Paint Company Limited) oder um fließfähige von Metall und Silicium freie organische Verbindungen handeln (vgl. DE-OS 2756495, offengelegt 22. Juni 1978, Shell International Research Maatschappij B. V.) oder auch um Gemische aus derartigen fließfähigen organischen Verbindungen und derartigen fließfähigen Organopolysiloxanen handeln. Auch zu Organopolysiloxanelastomeren vernetzbare Zweikomponentenmassen, die sowohl bei Raumtemperatur flüssige, durch Triorganosiloxygruppen endblockierte Diorganopolysiloxane oder andere nach dem Vernetzen der Masse noch fließfähige organische Verbindungen als auch stäbchenförmiges Mischpolymerisat aus Styrol und n-Butylacrylat enthalten, das durch Mischpolymerisation der genannten Monomeren mittels freier Radikale in Gegenwart von Diorganopolysiloxan erzeugt wurde, sind bereits bekannt (vgl. European Patent Application 0032597, veröffentlicht 29. Juli 1981, Shell Internationale Research Maatschappij B. V.).The substance which is still flowable after the crosslinking of the organopolysiloxane mass to form the elastomer can be diorganopolysiloxane which is liquid at room temperature and is blocked by triorganosiloxy groups (cf. GB-PS 14 70 465, published April 14, 1977, The International Paint Company Limited). or are flowable organic compounds free of metal and silicon (cf. DE-OS 2756495, published June 22, 1978, Shell International Research Maatschappij BV) or else mixtures of such flowable organic compounds and flowable organopolysiloxanes. Two-component also crosslinkable to form organopolysiloxane elastomers nentenmassen containing both diorganopolysiloxanes which are liquid at room temperature and blocked by triorganosiloxy groups or other organic compounds which are still flowable after crosslinking of the composition, and also rod-shaped copolymer of styrene and n-butyl acrylate which has been produced by copolymerizing the monomers mentioned with free radicals in the presence of diorganopolysiloxane , are already known (cf. European Patent Application 0032597, published July 29, 1981, Shell Internationale Research Maatschappij BV).

Die wichtigsten Beispiele für bei Raumtemperatur flüssige durch Triorganosiloxygruppen endblockierten Diorganopolysiloxane sind durch Trimethylsiloxygruppen endblockierte Dimethylpolysiloxane, durch Trimethylsiloxygruppen endblockierte Methylphenylsiloxane, durch Trimethylsiloxangruppen endblockierte Mischpolymerisate aus Dimethylsiloxan- und Methylphenylsiloxaneinheiten, durch Trimethylsiloxygruppen endblockierte Mischpolymerisate aus Dimethylsiloxan- und Diphenylsiloxaneinheiten und durch Trimethylsiloxygruppen endblockierte Mischpolymerisate aus Dimethylsiloxan-, Methylphenylsiloxan- und Diphenylsiloxaneinheiten.The most important examples of liquid at room temperature by triorganosiloxy end-blocked diorganopolysiloxanes are trimethylsiloxy endblocked dimethylpolysiloxanes end-blocked by trimethylsiloxy methyl phenyl end-blocked by trimethylsiloxane copolymers of dimethylsiloxane and methylphenylsiloxane endblocked by trimethylsiloxy copolymers of dimethylsiloxane and diphenylsiloxane and end-blocked by trimethylsiloxy copolymers of dimethylsiloxane, Methylphenylsiloxane and diphenylsiloxane units.

Die wichtigsten Beispiele für fließfähige von Metall und Silicium freie organische Verbindungen sind Polyisobutylene mit einem Molekulargewicht von 350 und technisches Weißöl sowie Trikresylphosphat.The most important examples of flowable organic compounds free of metal and silicon are polyisobutylenes with a molecular weight of 350 and technical white oil as well as tricresyl phosphate.

Der Stoff, der nach dem Vernetzen der Organopolysiloxanmasse zum Elastomeren noch fließfähig ist, ist in dieser Masse vorzugsweise in Mengen von 10 bis 80 Gewichtsprozent, bezogen auf das Gesamtgewicht von solchem Stoff, zu vernetzendem Organopolysiloxan und gegebenenfalls vorhandenem stäbchenförmigem Mischpolymerisat aus Styrol und n-Butylacrylat, vorhanden.The substance which is still flowable after the crosslinking of the organopolysiloxane composition to give the elastomer is preferably in this composition in amounts of 10 to 80 percent by weight, based on the total weight of such material, of the organopolysiloxane to be crosslinked and any rod-shaped copolymer of styrene and n-butyl acrylate present , available.

Die wichtigsten Beispiele für Vernetzer in Zweikomponentenmassen der im Rahmen der Erfindung verwendeten Art sind Polyethylsilikat mit einem Si02-Gehalt von 34 bis 40 Gew.% und Hexaethoxydisiloxan.The most important examples of crosslinkers in two-component compositions of the type used in the context of the invention are polyethylene silicate with an SiO 2 content of 34 to 40% by weight and hexaethoxydisiloxane.

Wichtigste Beispiele für Katalysatoren in Zweikomponentenmassen der erfindungsgemäß verwendeten Art sind Zinnverbindungen, wie Dibutylzinndilaurat und Dibutylzinndiacrylate, wobei sich die Acrylatgruppen jeweils von einem Gemisch aus 9 bis 11 Kohlenstoffatome je Molekül aufweisenden Carbonsäuren, worin die Carboxylgruppe bei mindestens 90 Gewichtsprozent der Säuren an ein tertiäres Kohlenstoffatom gebunden ist, ableiten (sogenanntes « Dibutylzinndiversatat »).The most important examples of catalysts in two-component compositions of the type used according to the invention are tin compounds, such as dibutyltin dilaurate and dibutyltin diacrylates, the acrylate groups each being composed of a mixture of carboxylic acids having 9 to 11 carbon atoms per molecule, in which the carboxyl group is bonded to a tertiary carbon atom in at least 90 percent by weight of the acids is derived (so-called «dibutyltin diversate»).

Die Herstellung von Schichten, die zumindest teilweise aus vernetztem Organopolysiloxan aus SiO4/2-Einheiten, Trimethylsiloxaneinheiten und Vinyldimethylsiloxaneinheiten bestehen, als Grundierungen ist bekannt und Zusammensetzungen zur Herstellung solcher Schichten sind im Handel erhältlich. Hierzu wird z. B. auf das Merkblatt « Wackersilicone » SM 12-121. 803, April 1980, Seite 1 und 2 verwiesen.The production of layers, which at least partially consist of crosslinked organopolysiloxane from SiO 4/2 units, trimethylsiloxane units and vinyldimethylsiloxane units, is known as primers and compositions for the production of such layers are commercially available. For this, z. B. on the leaflet "Wackersilicone" SM 12-121. 803, April 1980, pages 1 and 2.

Die Herstellung von Schichten aus Organopolysiloxanpolymer, das aus unter Ausschluß von Wasser lagerfähiger, bei Zutritt von Wasser bei Raumtemperatur vernetzender Masse hergestellt wurde, ist ebenfalls bekannt und vielfach beschrieben worden. Sie muß daher auch hier ebenfalls nicht mehr erläutert werden. Auch derartige Massen sind im Handel erhältlich. Bevorzugt unter den unter Ausschluß von Wasser lagerfähigen, bei Zutritt von Wasser bei Raumtemperatur vernetzenden Massen sind solche, bei deren Vernetzung Essigsäure oder Amin, wie sec.-Butylamin oder Cyclohexylamin, frei wird.The production of layers of organopolysiloxane polymer which has been prepared from a composition which can be stored with the exclusion of water and which crosslinks when water is admitted at room temperature is also known and has been described many times. Therefore, it does not have to be explained here either. Such compositions are also commercially available. Preferred among the masses which can be stored in the absence of water and which crosslink when water is admitted at room temperature are those which, when crosslinked, release acetic acid or amine, such as sec-butylamine or cyclohexylamine.

Die bei dem erfindungsgemäßen Verfahren eingesetzten Grundiermittel können in einem organischen Lösungsmittel, wie Toluol oder einem Gemisch aus Xylolisomeren, gelöst bzw. dispergiert sein. Ebenso können die bei dem erfindungsgemäßen Verfahren eingesetzten, zu Organopolysiloxanelastomeren vernetzbaren Zweikomponentenmassen in einem organischen Lösungsmittel, wie Testbenzin, gelöst bzw. dispergiert sein.The primers used in the process according to the invention can be dissolved or dispersed in an organic solvent, such as toluene or a mixture of xylene isomers. Likewise, the two-component compositions which can be crosslinked to give organopolysiloxane elastomers in the process according to the invention can be dissolved or dispersed in an organic solvent, such as white spirit.

Das Auftragen der im Rahmen des erfindungsgemäßen Verfahrens eingesetzten Mischungen auf die Unterlagen kann z. B. durch Streichen, Gießen, Sprühen oder Aufwalzen erfolgen.The application of the mixtures used in the process according to the invention on the documents can, for. B. by brushing, pouring, spraying or rolling.

In dem folgenden Beispiel und Vergleichsversuch beziehen sich alle Angaben von Teilen und Prozentsätzen auf das Gewicht, soweit nichts anderes angegeben ist.In the following example and comparative experiment, all parts and percentages are by weight, unless stated otherwise.

Beispielexample

Auf Stahlblech wird Haftlack auf der Basis Epoxid-Teer aufgetragen. 72 Stunden nach diesem Auftragen wird auf diese Schicht durch Tauchen eine Mischung aus

  • 10 Teilen Polyethylsilikat mit einem Si02-Gehalt von etwa 34 %
  • 10 Teilen Butyltitanat
  • 10 Teilen eines Organopolysiloxans aus SiO4/2-Einheiten, Trimethylsiloxaneinheiten und Vinyldimethylsiloxaneinheiten im Molverhältnis von 1 : 0,8 : 0,1

in Form einer 60 %-igen Lösung in Toluol aufgetragen.Adhesive varnish based on epoxy tar is applied to steel sheet. 72 hours after this application, a mixture is dipped onto this layer by dipping
  • 10 parts of polyethylene silicate with an Si0 2 content of about 34%
  • 10 parts of butyl titanate
  • 10 parts of an organopolysiloxane composed of SiO 4/2 units, trimethylsiloxane units and vinyldimethylsiloxane units in a molar ratio of 1: 0.8: 0.1

applied in the form of a 60% solution in toluene.

Eine Stunde nach dem Auftragen dieser Organopolysiloxan enthaltenden Mischung wird auf die aus dieser Mischung erzeugte Schicht als unter Ausschluß von Wasser lagerfähige, bei Zutritt von Wasser bei Raumtemperatur zu einem Elastomeren vernetzende Masse eine solche aufgetragen, die durch Vermischen von

  • 100 Teilen eines in den endständigen Einheiten Si-gebundene Hydroxylgruppe aufweisenden Dimethylpolysiloxans mit einer Viskosität von etwa 80 000 mPa - s bei 25 °C mit
  • 20 Teilen eines Siliciumdioxyds mit einer Oberfläche von 150 m2/g, dessen Silanolgruppen teilweise durch Trimethylsiloxygruppen ersetzt sind,
    Figure imgb0001
    hergestellt worden ist,
    aufgetragen. Zwei Stunden nach dem Auftragen dieser Masse wird auf die daraus erzeugte Schicht als zum Elastomeren vernetzbare Masse, die zusätzlich zu Diorganopolysiloxan, das vernetzbar ist, Vernetzungsmittel und Katalysator als mindestens einen weiteren Bestandteil einen Stoff enthält, der nach dem Vernetzen der Masse noch fließfähig ist und wobei Vernetzungsmittel und Katalysator erst mehr oder weniger kurz vor dem Auftragen der Masse auf die Grundierung eingemischt wurden, eine Mischung aus
  • 100 Teilen eines Gemisches, das seinerseits aus
  • 62,5 Teilen eines in den endständigen Einhei- . ten je eine Si-gebundene Hydroxylgruppe aufweisenden Dimethylpolysiloxans mit einer Viskosität von etwa 1 000 mPa - s bei 25 °C
    Figure imgb0002
    besteht,
  • 20 Teilen eines durch Trimethylsiloxygruppen endblockierten Dimethylpolysiloxans mit einem mittleren Molekulargewicht von etwa 16000
    und kurz vor dem Auftragen eingemischten
  • 3 Teilen eines Gemisches, das seinerseits aus
  • 3 Teilen Polyethylsilikat mit einem SiOZ' Gehalt von etwa 34 %
  • 1 Teil Dibutylzinndiacrylaten, wobei sich die Acrylatgruppen jeweils von einem Gemisch aus 9 bis 11 Kohlenstoffatomen je Molekül aufweisenden Carbonsäuren ableiten, worin die Carboxylgruppe bei mindestens 90 % der Säuren an ein tertiäres Kohlenstoffatom gebunden ist, besteht,

mittels eines Streichmessers aufgetragen. Auf diese Beschichtung wird vor dem Beginn ihrer merklichen Vernetzung ein dünner, mit dem oben angegebenen Haftlack beschichteter und dann in gleicher Weise wie oben angegeben weiterhin beschichteter Stahlblechstreifen ebenfalls vor dem Beginn der merklichen Vernetzung der zum Elastomeren vernetzbaren Masse überlappend gelegt und leicht angedrückt.One hour after the application of this mixture containing organopolysiloxane, one is applied to the layer produced from this mixture as a storable composition with the exclusion of water and crosslinking to an elastomer when water is added at room temperature, which is obtained by mixing
  • 100 parts of a dimethylpolysiloxane having Si-bonded hydroxyl group in the terminal units and having a viscosity of about 80,000 mPa.s at 25 ° C.
  • 20 parts of a silicon dioxide with a surface area of 150 m 2 / g, its silanol groups are partially replaced by trimethylsiloxy groups,
    Figure imgb0001
    has been manufactured
    applied. Two hours after the application of this mass, the resulting layer is crosslinkable to form the elastomer, which, in addition to diorganopolysiloxane, which is crosslinkable, contains crosslinking agent and catalyst as at least one further constituent, which is still flowable after the crosslinking of the mass and the crosslinking agent and catalyst being mixed in more or less shortly before the composition was applied to the primer, a mixture of
  • 100 parts of a mixture, which in turn consists of
  • 62.5 parts of one in the terminal units. each have a Si-bonded hydroxyl group-containing dimethylpolysiloxane with a viscosity of about 1,000 mPa.s at 25 ° C
    Figure imgb0002
    consists,
  • 20 parts of a dimethylpolysiloxane endblocked by trimethylsiloxy groups with an average molecular weight of about 16,000
    and mixed in just before application
  • 3 parts of a mixture, which in turn consists of
  • 3 parts of polyethylene silicate with an SiO Z ' content of about 34%
  • 1 part of dibutyltin diacrylates, the acrylate groups each being derived from a mixture of 9 to 11 carbon atoms per molecule having carboxylic acids, in which the carboxyl group is bonded to a tertiary carbon atom in at least 90% of the acids,

applied with a doctor knife. A thin steel sheet strip, coated with the above-mentioned adhesive varnish and then coated in the same manner as above, is also overlapped and lightly pressed onto this coating before the beginning of its noticeable crosslinking.

Die so erhaltene Anordnung wird 7 Tage bei 23 °C und einem relativen Wassergehalt der Luft (« Luftfeuchte •) von 50 % gelagert. Danach wird der Blechstreifen mit einer Geschwindigkeit von 200 mm/Minute abgezogen. Die dabei bestimmte Scherhaftung beträgt 116 N/cm2.The arrangement obtained in this way is stored for 7 days at 23 ° C. and a relative water content of the air (“air humidity •) of 50%. The sheet metal strip is then removed at a speed of 200 mm / minute. The determined shear adhesion is 116 N / cm 2 .

VergleichsversuchComparison test

Die im Beispiel angegebene Arbeitsweise wird wiederholt mit der Abänderung, daß als Grundierung eine Mischung aus

Figure imgb0003
in Form einer 10 %-igen Lösung in Testbenzin verwendet wird.The procedure given in the example is repeated with the modification that a mixture of as a primer
Figure imgb0003
 in the form of a 10% solution in white spirit.

Die wie im Beispiel angegeben nach dem siebentägigen Lagern bei 23 °C und 50 % Luftfeuchte bestimmte Scherhaftung beträgt 92,4 N/cm2.The shear adhesion, determined in the example after seven days of storage at 23 ° C. and 50% atmospheric humidity, is 92.4 N / cm 2 .

Claims (2)

1. Process for strengthening the adhesion of organopolysiloxane elastomers, produced from compositions that can be cross-linked at room temperature, to supports, by applying a base coating to the support before applying the composition that can be cross-linked to form the elastomer, this composition containing, in addition to cross-linkable diorganopolysiloxane, a cross-linking agent and a catalyst, as at least one further constituent or as at least one component of further constituents, a substance that is still capable of flowing after cross-linking has taken place, or a rod-shaped copolymer of styrene and n-butyl acrylate which is produced by copolymerising the said monomers by means of free radicals in the presence of diorganopolysiloxane, or containing both a copolymer of that type and a substance that is still capable of flowing after the composition has been cross-linked, and the cross-linking agent and the catalyst being mixed into the composition only more or less shortly before the composition is applied to the base coating, characterised in that there is used as the base coating a layer that consists at least partly of a cross-linked organopolysiloxane having Si0412 units, trimethylsiloxane units and vinyl- dimethylsiloxane units, and a layer of an organopolysiloxane elastomer that is applied to the former layer and is at least partially cross-linked, which organopolysiloxane elastomer is produced from a composition that can be stored with the exclusion of water and that cross-links on the admission of water at room temperature.
2. Process according to claim 1, characterised in that there is used as the composition that can be stored with the exclusion of water and that cross-links on the admission of water at room temperature, one that frees acetic acid or an amine on cross-linking.
EP19830102615 1982-03-17 1983-03-17 Process for modifying the bonding of siloxane elastomer Expired EP0089066B1 (en)

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DE19823209755 DE3209755A1 (en) 1982-03-17 1982-03-17 METHOD FOR REINFORCING THE ADHESION OF ORGANOPOLYSILOXANELASTOMERS
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6013754A (en) * 1998-01-16 2000-01-11 Courtaulds Coatings, Inc. Heavy Duty Division Catalyst free primer coating compositions

Families Citing this family (32)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4133566A (en) * 1977-06-23 1979-01-09 Miller Robert B High pressure duct clamp and method of use
GB8319300D0 (en) * 1983-07-16 1983-08-17 Ciba Geigy Ag Treating textiles
JPS60233153A (en) * 1984-05-04 1985-11-19 Toray Silicone Co Ltd Primer composition
DE3418406A1 (en) * 1984-05-17 1985-11-21 Wacker-Chemie GmbH, 8000 München METHOD FOR REINFORCING THE ADHESION OF ELASTOMERS AND COATINGS PRODUCED BY THIS METHOD
US4564562A (en) * 1984-05-29 1986-01-14 At&T Technologies, Inc. Silicone encapsulated devices
US4592959A (en) * 1984-11-19 1986-06-03 At&T Technologies, Inc. Silicone encapsulated devices
US4810768A (en) * 1984-11-19 1989-03-07 American Telephone And Telegraph Company Method and formulation for extending shelf life of a silicone resin
JPH0768495B2 (en) * 1989-08-15 1995-07-26 信越化学工業株式会社 Method for manufacturing integrally molded product with silicone rubber bonded
US4988759A (en) * 1989-09-26 1991-01-29 E. I. Du Pont De Nemours And Company Coating composition of acrylic polymers containing reactive groups and an epoxy organosilane
US5064719A (en) * 1989-09-26 1991-11-12 E. I. Du Pont De Nemours And Company Coating composition of acrylic polymers containing reactive groups and an epoxy organosilane
US5175028A (en) * 1990-01-23 1992-12-29 Konica Corporation Method of forming layers on a support
DK0521983T3 (en) * 1990-03-27 1994-11-14 Courtaulds Coatings Holdings coating Material
US5270110A (en) * 1990-07-19 1993-12-14 Dow Corning Toray Silicon Co., Ltd. Film-forming organopolysiloxane composition
JP2994699B2 (en) * 1990-07-19 1999-12-27 東レ・ダウコーニング・シリコーン株式会社 Film-forming organopolysiloxane composition
US5567235A (en) * 1990-08-30 1996-10-22 Elf Atochem North America, Inc. Method for strengthening a brittle oxide substrate, silane-based compositions, and a polymerized cross-linked siloxane coated brittle oxide substrate
US6013333A (en) * 1990-08-30 2000-01-11 Elf Atochem North America, Inc. Method for strengthening a brittle oxide substrate
US5213617A (en) * 1991-06-13 1993-05-25 Dow Corning Corporation Primer for silicone substrates
US5238708A (en) * 1991-06-13 1993-08-24 Dow Corning Corporation Primer for silicone substrates
US5192603A (en) * 1991-09-13 1993-03-09 Courtaulds Coatings Inc. Protection of substrates against aquatic fouling
WO1993006180A1 (en) * 1991-09-13 1993-04-01 Courtaulds Coatings (Holdings) Limited Protection of substrates against aquatic fouling
DE69314997T2 (en) * 1992-06-19 1998-03-05 Fuji Polymertech Co Ltd Method for producing a finger button for a hand switch
CN1040989C (en) * 1993-07-15 1998-12-02 中国科学院兰州化学物理研究所 Nontoxic marine pollution-free coating
CN1040448C (en) * 1993-07-15 1998-10-28 中国科学院兰州化学物理研究所 Pollution-free marine coating
CN1040990C (en) * 1993-07-15 1998-12-02 中国科学院兰州化学物理研究所 Single-component pollution-free coating
US5691019A (en) * 1995-05-01 1997-11-25 General Electric Company Foul release system
DE19545363A1 (en) * 1995-12-05 1997-06-12 Wacker Chemie Gmbh Low molecular weight organosilicon compounds, processes for their preparation and their use in crosslinkable organopolysiloxane compositions
GB9704794D0 (en) * 1997-03-07 1997-04-23 Courtaulds Coatings Holdings Fouling inhibition
GB9727261D0 (en) 1997-12-23 1998-02-25 Courtaulds Coatings Holdings Fouling inhibition
EP1168372B1 (en) * 2000-06-20 2006-10-04 Abb Research Ltd. Resin for electrical insulation
US20030129397A1 (en) * 2001-09-07 2003-07-10 Wilson Daniel A. Coated optical fibers using adhesion promoters, and methods for making and using same
SG156665A1 (en) * 2006-02-17 2009-11-26 Chugoku Marine Paints Curable organopolysiloxane composition and antifouling composite coating film
ES2622405T3 (en) 2009-12-23 2017-07-06 Dsm Ip Assets B.V. Method to activate silicone rubber surfaces

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3022196A (en) * 1962-02-20 Coating and adhesive composition
US3317369A (en) * 1961-04-07 1967-05-02 Dow Corning Acryloxyalkylsilane compositions and the fabrication of structures therewith
US3691206A (en) * 1965-09-29 1972-09-12 Hal J Northrup Primer for cured silicone release agents
US3816164A (en) * 1967-12-06 1974-06-11 Stauffer Chemical Co Substrate coated with a room temperature curable organopolysiloxane and method for coating
US3702778A (en) * 1970-03-23 1972-11-14 Battelle Memorial Institute Ship's hull coated with antifouling silicone rubber
US3677998A (en) * 1970-04-09 1972-07-18 Dow Corning Primer for adhesion of silicone rubber to metal
JPS5139673B2 (en) * 1972-07-14 1976-10-29
US4243718A (en) * 1978-11-24 1981-01-06 Toshiba Silicone Co. Ltd. Primer compositions for Si-H-olefin platinum catalyzed silicone compositions
EP0032597B1 (en) * 1979-12-11 1983-11-30 Shell Internationale Researchmaatschappij B.V. Coated marine structure
JPS56103264A (en) * 1980-01-21 1981-08-18 Toray Silicone Co Ltd Silicone compositin for adhesive

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6013754A (en) * 1998-01-16 2000-01-11 Courtaulds Coatings, Inc. Heavy Duty Division Catalyst free primer coating compositions

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